Metallizable trisazo dyestuffs



United States Patent:

METALLIZABLE TRISAZO DYESTUFFS Marcel Reding, Basel, and Werner Bossard, Riehen, near Basel, Switzerland, assignors to J. R. Geigy A. G., Basel, Switzerland, a Swiss firm N Drawing. Application September 14, 1953, Serial No. 380,127

Claims priority, application Switzerland October 16, 1952 8 Claims. (Cl. 260-173) The present invention concerns the production of new, metallisable trisazo dyestuifs, the coppered cellulose dyeings of which have very good fastness properties. They dye cellulose material by the direct dyeing method in yellow-green, green to olive green shades which are not changed much by the coppering process. Coppered cellulose dyeings are obtained according to the composition of the dyestufr', some of which have such excellent fastness to washing that they withstand repeated soap washings. The dyestuffs according to this invention supplement the group of fast, copperable trisazo dyestuffs at a point where at present there are not sufficient dyestuffs to fulfill the high demands made upon them.

it has now been found that valuable trisazo dyestuffs of the type (FYI acyl can be obtained, if a diazotised amino compound of the benzene series (A) containing a hydroxyl group or a substituent which can be converted into a hydroxyl group in the o-position to the diazo group, is coupled with a new middle component of the composition which middle component will be more fully described below, diazotising the aminoazo dyestuff so obtained and coupling the diazo compound in an acid medium with a l-aminonaphthalene compound (D) coupling in the 4-position which contains a substituent in the 2-position suitable for the formation of the metal complex, in particular an alkoxy group. This can also be further substituted if desired, preferably by a carboxyl group. The aminodisazo dyestuff is then again diazotised and cou pled in an alkaline medium with a 2-acylamino-6-hydroxynaphthalene-8-sulphonic acid (E).

In this middle component of the above Formula II containing the radical B, each of 211 and n2 represents an integer of the value of i) and l, X represents the direct carbon-to-carbon linkage or a CO-NH or a group, one Y1 and Y2 represents hydrogen and the other represents an acyi-Cl-lz-CO group, wherein acyl means an alkoyl or a benzoyl radical. All the benzene rings in this formula as well as in all formulae derived therefrom can contain the non-ionogenic substituents usual in azo dyestuffs, for example, halogen, alkyl, or alkoxy groups. These new middle components used according to the present invention (corresponding to B) are monoprimary amino compounds which are derived from polynuclear, substantive diamino compounds of the diphenyl, diphenyl urea and benzanilide series having a sulphonic acid group standing in the o-position to an amino group and wherein an amino group is acyloacetylated. The 4,4-diaminodiphenyl 3 sulphonic acids, 4,4- or 4,3-diaminodiphenyl urea-S-sulphonic acids and 4-(3- or 4 arninobenzoylarnino) 1 aminobenzene-2- sulphonic acids can be used chiefly as starting materials for the production of the middle components. Also derivatives of these compounds can be used, one amino group of which is substituted by a 3- or 4-aminobenzoyl SOsH or aminophenylcarbamyl group, but the dinuclear compounds are more suited to the process of the present invention. The further substitution of the benzene rings has been dealt with above. If acyloacetylating agents, e. g. diketene is reacted in the cold with the aqueous solutions of their alkali salts then, in a single reaction, only the amino group in the benzene ring having no sulphonic acid groups is acyloacetylated. The middle components so obtained produce trisazo dyestuffs according to the present invention which are particularly fast to acid. It is also possible to react acyloacetylating agents in the warm with the aqueous solutions of the alkali salts of 4-(3- or 4-nitrobenzoyl or nitrophenylcarbamylamino) l-aminobenzene-Z-sulphonic acids, preferably diketene at 4G-60 C., until the primary amino groups have disappeared and thus, after reduction of the nitro groups to amino groups, middle components of Formula II usable according to the process of the present invention are obtained. In these compounds also the primary amino groups can again be acylated with 3- or 4-nitrobenzoyl chloride or with 3- or 4-nitrophenyl isocyanate and then the nitro groups can be reduced to primary amino groups. However, in this group also, dinuclear compounds are to be preferrd to polynuclear.

Particularly pure trisazo dyestuffs according to the present invention are obtained with such middle components of the general Formula II which have a benzene ring wherein the substituents as defined are in the m-position.

If diazotised o-hydroxyamino compounds of the benzene series are reacted in an alkaline medium with com pounds of the Formula II, the coupling occurs in the acyloacetyl radical and metallisable amiuo-monoazo dyestuffs which can be further diazotised are obtained.

As starting components, those 2amino-l-hydroxybenzene compounds usable in metallisable azo dyestuffs can be used. These compounds can contain further substituents, e. g. halogen, alkyl, alkoxy, carboxyl sulphonic acid, sulphonic acid amide and carboxylic acid amide groups organically substituted at the nitrogen atom, alkyl sulphonyl, aryl sulphonyl and acylarnino groups.

Z-alkoxy-1-aminonaphthalene compounds coupling in the 4-position can be used as the second coupling components D, e. g. l-amino-Z-methoxyor ethoxy-naphthalene, 1-amino-2 naphthylglycolic acid and derivatives thereof sulphonated in the 6- or 7-position of the naphthalene ring. l-amino 2 naphthyl-glycolic acid often has a favourable influence on the drawing power of the trisazo dyestuffs according to the present invention, and is therefore, to be preferred.

The 2 acylamino 6 hydroxynaphthalene 8 sulphonic acids used as end components E can contain as acyl radicals alkoyl radicals derived from lower fatty acids which can be further substituted, e. g. acetyl-, propionyl, butyryl, chloracetyl, 2-bromopropionyl, methoxyacetyl, dimethylacryl, succinyl radicals or aroyl radicals, preferably of the benzene series, e. g. benzoyl, 4- or Z-methylor chlorobenzoyl, 4- or 3-aminobenzoyl, 4 or 3-acetamidobenzoyL 4-chloro or methoxy or methyl- 3-aminobenzoyl, 4-methoxyor ethoxybenzoyl radicals, further radicals of alicyclic or heterocyclic carboxylic acids as Well as acyl radicals derived from carbonic acid such as carbamyl and carbalkoxy radicals, e. g. the dimethylcarbamyl or a phenylcarbamyl group or the carbethoxy, carbomethoxy, the carbomethoxy-ethoxy group. The final coupling is advantageously performed in an alkaline medium in the presence of tertiary organic bases, e. g. in the presence of pyridine and homologues thereof.

The present invention, in its broadest sense, comprises trisazo dyestuffs of the general Formula I wherein B corresponds to the radical of a middle component of Formula II. More easily available are the dinuclear middle components of the Formula II, wherein 112 has the value of 0. In a more valuable class of trisazo'dyestutfs according to the present invention therefore, B represents the radigroups, X represents a bridging member selected from the cal of a middle component of the general Formula 111: group consisting of the direct carbon-carbon linkage and YPNH SOSH the groups CONH- and -NH-CO-NH, acyl represents a member selected from the group consisting X 5 of alkoyl and benzoyl radicals, Y represents a member 2 (111) selected from the group consisting of alkoXy and OCH2COOH groups, one Z represents hydrogen and the SYIIEWS have the meanings given for Formula the other Z represents a member selected from the group jl nllddle components of the general Formula consisting of hydrogen and the sulphonic acid group, and II Whlch 0011mm the l'adleali R represents a carboxylic acid acyl radical bound directly S0311 to the adjacent NH group by the CO group.

l In the form of their alkali salts, the new trisazo dyestuffs dissolve in hot water with a green colour and they dye cellulose fibres direct from a dyebath containing 15 Glaubers salts in olive green, yellow-green to green Produce Partlculafly Valuable dyestuffs Thus m the shades. The shade is only slightly altered on after-treatrnost valuable group of dyestuffs according to the present ing the cellulose dyeing with agents giving Off copper, on mventwn of the general Formula B represents the the other hand the fastness to wet and light is considerliadlcal 0 compound of the general Formula 1V ably improved. The coppering process can be performed HWPCHVO SOaH in a neutral to weakly acid medium in the dyebath or in a l fresh bath with the usual copper salts such as, e. g. O copper acetate or copper sulphate. If desired, copper compounds can be used which are stable to alkali such as are obtained by reacting copper sulphate with sodium wherein X represents the groups CO-NH or tartrate in a sodafalkaline bath.

The following examples illustrate the Invention without limiting it in any way. Where not otherwise stated, The trisazo dyestuffs of the invention can also be departs are given as parts by weight and the temperatures fined as corresponding to the formula are in degrees centigrade. The relationship of parts by SOaH Sit OH OH aeyl .i-N=N-( JH-o O-NH- B -VX -N=N --N=N s 0 3H l I z z NH-R wherein A represents an aromatic radical of the benzene weight to parts by volume is as that of kilogrammes to series containing the hydroxyl group in the o-position litres. to the azo linkage, each of n and m is one of the numbers Example 1 O and 1, B stands for the group 18.7 parts of 2-am1no-l-hydroxybenzenel-methyl sul- S|O3H phone are dissolved With 15 parts of concentrated hy- I" drochloric acid in 200 parts of water and diazotised at I; 10 with 6.9 parts of sodium nitrite. The resulting suspension is poured into a solution of 41 parts of 5-(3'- each of U andV represents an aromahc radical of the acetoacetylaminobenzoylamino) 2 aminobenzene 1. benzene series in which the bonds shown stand in other sulphonic acid i 400 parts f water d 24 parts f h the o'pesition 0f 5aid ammatie radleels e Whleh dium bicarbonate. On completion of the coupling the are free from carbmryhc acid and sulphomc acid groups, yellow monoazo d t ff i l d out d fil d ff, X represents a s s member Selected f the -PP The filter cake is dissolved in 1000 parts of water and consisting of the (llICC't carbon-carbon linkage and the 9 parts f Sodium nitrite are dd A ll di groups and s suspension is obtained by the dropwise addition of 40 represents a member Selected from the group eenslstmg parts of concentrated hydrochloric acid at 10-15, which of alkoyl and benzoyl radicals, Y represents a member is made Weakly acid to Congo red ft Stirring f 4 Selected {mm the group consisting of alkoxy and hours with 5 arts of sodium carbonate t is then cou- --OCH2COOH groups, one Z represents hydrogen and p l f the other Z represents a member selected from the group i fi g g 3?} emu]? P consisting of hydrogen and the sulphonic acid group, gyco ac] e 5 0 so ace 0 and R represents a carboxylic acid acyl radical bound eelerate the leaetlon, Paris of seelum earbenate ale directly to the adjacent group by the 5 added to keep the reaction slightly acid. The disazo dyestuff formed is dissolved with 5 parts of caustic soda,

They may also be defined as correspond ng to the muted With 400 parts Of sodium chloride, 60 parts Of formula concentrated hydrochloric acid and diazotised with 8.2

SOaH Y OH (|)H acyl I A-N=N-( JHGONH V-X N=N- -N=N -SO:H

z l I'm-R wherein A represents an aromatic radical of the benzene parts of sodium nitrite at 20. On cornpletion of the series containing the hydroxyl group in the o-position diazotisation, the diazo compound is filtered off and to the azo linkage, V represents an aromatic radical of washed. it is then coupled with 34.3 parts of Z-benzoylthe benzene series in which the bonds shown stand in amino-6-hydroxynaphthalene-S-sulphomc acid in 200 other than the o-position of said aromatic radical and parts of water in the presence of 150 parts of pyridine which is free from carboxylic acid and sulphomc acid and 20 parts of sodium carbonate.

is precipitated with a little sodium chloride, filtered oil and freed from adhering impurities by washing.

It is a dark powder which dissolves in water with a green and in concentrated sulphuric acid with an olive green colour. It dyes fibres from natural or regenerated cellulose in vivid yellowish-green shades. The dyeings are made fast to light, washing and acid by after-treatment with copper salts.

if, in this example 10.9 parts of Z-amino-l-hydroxybenzene or 12.5 parts of 4-methyl-2-arnino-l-l1ydroxy benzene or 18.9 parts of 2-amino-1hydroxybenzene-4- sulphonic acid or 20.5 parts of 6-methyl-2-amino-l-hydroxybenzenel-suiphonic acid or 22.4 parts of fi-chloro- 2-aminol-hydroxybenzene-4-sulphonic acid or 21.6 parts of Z-arnino-l-hydroxybenzene-4-sulphonic acid ethyl amide or 24.4 parts of 2-amino-l-hydroxybenzene-4- sulphonic acid-diethylamide or 27.5 parts of 2-amino-lhydroxybenzenelsulphonic acid-diethanolamide, or 21.6 parts of 2-amino-1-hydroXybenZene-4-su[phonic acid-dimethylamide or 18.8 parts of Z-amino-l-hydroxybenzene- 4-sulphonic acid amide or 15.3 parts of Z-amino-l-hydroxybenzenel-carboxylic acid or 20.8 parts of Z-amino- 1-hydroxybenzene-4-carboxylic acid-diethylamide or 24 parts of Z-amino-l-hydroxybenzene-4-carboxylic acid-diethanolamide or 22.8 parts of 2amino-l-hydroxybenzene- 4-carbcxylic acid-phenyla-rnide or 22.2 parts of 6-chloro- 2-amino-1-hydroxybenzene-4-methyl sulphone or 24.4

parts of 6 acetylamino 2 amino 1 hydroxybenzene- 4-methyl sulphone are used instead of 18.7 parts of 2- amino-1-hydroxybenzene-4-methyl sulphone, analogous green trisazo dyestufis are obtained which have similar properties.

Example 2 24.4 parts of 2-amino-1-hydroxybenzene-4-sulphonic acid-dimethyiarnide are dissolved at 50 with 7.5 parts of sodium carbonate in 500 parts of water. 6.9 parts of sodium nitrite are added and the solution is poured at on to 30 parts of concentrated hydrochloric acid. The diazonium solution is poured into 40.6 parts of 3- acetoacetylamino 4 amino 1.1 diphenyl urea 3- sulphonic acid in 400 parts of water and 24 parts of sodium bicarbonate. The yellow monoazo dyestufl? is isolated, dissolved in 1000 parts of water and diazotised at 1015 with 6.9 parts of sodium nitrite and 40 parts of concentrated hydrochloric acid. The diazonium compound neutralised with 4 parts of sodium carbonate is poured at 0-5" into a solution of 21.7 parts of l-amino- 2-naphthyl glycolic acid to which has been added parts of sodium acetate. The reaction of the coupling is kept weakly acid by the addition of 5 parts of sodium carbonate. The violet disazo dyestuif dissolves with 5 parts of caustic soda and is further diazotised as described in Example 1. The isolated diazonium compound can be coupled with 34.8 parts of 6-hydroxynaphthyl- COCHs 802GB! (2)-carbamic acid-methoxyethyl ester-8-sulphonic acid in OCHzCOOH OH I lI-[CO 200 parts of water with the addition of 20 parts of sodium carbonate and parts of pyridine to form the green trisazo dyestuif of the formula:

HOOCCHzO O NHCOOCHaCHzOCHa It is a dark powder which dissolves in water with a green and in concentrated sulphuric acid with an olive green colour. It dyes cotton, rayon, viscose, hemp and jute in green shades. After treatment with copper compounds according to one of the usual methods, the dyeings have very good fastness properties.

it in this example the 24.4 parts of Z-amino-l-hydroxybenzene-4-sulphonic acid dimethyl amide are replaced by 18.7 parts of Z-amino-l-h.ydroXybenzene-4- methyl sulphone, 10.9 parts of Z-amino-l-hydroxybenzene, 12.5 parts of 4-methyl-2-amino-l-hydroxybenzene, 18.9 parts of Z-amino-l-hydroxybenzene-4-sulphonic acid, 20.5 parts of 6-rnethyl-2-amino-l-hydroxybenzenc- 4-sulphonic acid, 22.4 parts of 6-chloro2-amino-1-hydroxybenzene-4-sulphonic acid, 21.6 parts of Z-amino- 1-hydroxybenzene l-sulphonic acid-ethyl amide, 27.5 parts of Z-arnino-l-hydroxybenzenel-sulphonic acid-diethanolamide, 18.8 parts of Z-amino-l-hydroxybenzene- 4-sulphonic acid amide, l5 .3 parts of Z-amino-l-hydroxybenzene-4-carboxylic acid, 20.8 parts of 2-amino-l-hydroxybenzenel-carboxylic acid-diethyl amide, 24 parts of Z-amino-1-hydroxybenZene-4-carooxylic acid-diethanol amide, 22.8 parts of 2-aminol-hydroxybenzene-4-carboxylic acid-phenyl amide, 16.6 parts of 4acetylamino-2- amino-l-hydroxybenzene, 24.4 parts of 6-acetyl-amino- 2-amino-l-hydr0Xybenzene-4-rnethyl sulphone or 22.2 parts of 6-chloro-2-amino-1-hydroxybenzene-4'methyl sulphone, similar green trisazo dyestuifs are obtained which have similar properties.

Example 3 18.7 parts of Z-amino-l-hydroxybenzene-4-methylsulphone are diazotised as described in Example 1, and the diazo compound is poured into a solution of 40.6 parts of 3-acetoacetyiami11o-4-amino-1.1-diphenyl urea- 3-sulphonic acid in 400 parts of water and 30 parts of sodium carbonate. The -rnonoazo dyestuif which'has been isolated and 6.9 parts of sodium nitrite are dissolved in 1000 parts of water and the whole is poured at 'l0-15 on to 40 parts of concentrated hydrochloric acid. After stirring for 4 hours, the diazoniurn compound which precipitates is filtered off and added to a solution of 21.7 parts or l-amino-2-naphthylglycolic acid in 600 parts of water to which has been added 20 parts of sodium acetate. The violet disazo dyestufll is further diazotised as described in Example 1, filtered, and coupled with a solution of 35.8 parts of 2-(3'-amino-benzoylamino)-6-hydroxynaphthalene8-sulphonic acid in 200 parts of water in the presence of 20 parts of sodium carbonate and 150 parts of pyridine to form the trisazo dyestuff of the formula:

HOOCCHzO O The dyestufifis precipitated with a little sodium chloride, filtered and washed with diluted sodium chloride solution. When dry, it is a dark powder which dissolves in water with a green and in concentrated sulphuric acid with a brown-olive colour. After treating with copper salts, dyeings on natural or regenerated cellulose are of green shades which have excellent fastness properties.

If in the above example the 35.8 parts of 2-(3'-aminobenzoylamino)-6-hydroxynaphthalene 8 sulphonic acid are replaced by 34.3 parts of Z-benzoylamino-6-hydroxynaphthalene-S-sulphonic acid or 28.1 parts of 2-acetylamino-6-hydroxynaphthalene-8-sulphonic acid or 35.8 parts of 2- (4-aminobenzoylamino)-6-hydroxynaphtha lene-8-sulphonic acid or 39.3 parts of 2-(4-chloro-3- aminobenzoylamino)- 6 -hydroxynaphthalene-8-sulphonic acid or 37.9 parts of 2-(2- or -4'-chlorobenzoylamiuo)- 6-hydroxynaphthalene-8-sulphonic acid or 41.2 parts of 2 (2.4-dichloro-benzoylamino)-6-hydroxynaphthalene- 8-sulphonic acid or 37.2 parts of 2-(4-methyl-3-aminobenzoylamino)-6-hydroxynaphthalene-8-sulpl1onic acid or 38.8 parts of 2-(4-methoxy-3-aminobenzoylamino)-6- hydroxynaphthalene-8-sulphonic acid or 40 parts of 2- (3 acetylaminobenzoylamino)-6-hydroxynaphthalcne-8- sulphonic acid or 36.9 parts of 2-cinnamoylamino-6-hydroxynaphthalene-8-sulphonic acid or 33 parts of 2- furanoylamino-6-hydroxynaphthalene-8-sulphonic acid or 32.1 parts of 2-(5.13-dimethyl-acrylamino)-6-l1ydroxynaphthalene-8-sulphonic acid or 29.7 parts of 2-carbomethoxyamino-6-hydroxynaphthalene-8-sulphonic acid or 31.1 parts of 2-carbethoxyamino-6-hydroxynaphthalene- 8-sulphonic acid, similar dyestuffs with the same properties are obtained.

Example 4 of 21.7 parts of 1-amino-2naphthylglycolic acid and 20 parts of sodium acetate in 600 parts of water. 4 parts of sodium carbonate are added until there is a weakly acid reaction to accelerate the coupling. The violet disazo dyestuff is further diazotised with 60 parts of hydrochloric acid and 8.2 parts of sodium nitrite at 20, filtered and coupled with 28.1 parts of 2-acetylamino-6- hydroxynaphthalene-8-sulphonic acid and 20 parts of sodium carbonate in 200 parts of water, 150 parts of pyridine to form the trisazo dyestuff of the formula:

The dyestuff is a daik powder which dissolves in water with a green colourand. in concentrated sulphuric acid with a greenish brown colour. regenerated cellulose fibres in green shades. On aftertreating with copper salts on the fibre the shade does not change much but "the dyeings have very good washing,

It dyes natural and SOaH light and acid fastness properties. If in the above example the 42 parts of 3-acetoacetylamino-4-methyl-4- amino-l.l'-diphenyl urea-3-sulphonic acid are replaced by 40.6 parts of 3- or 4-acetoacetylamino-4-amino-1.1- diphenyl urea-3-sulphonic acid, 39.1 parts of 1-(3'- or 4- acetoacetylaminobenzoylamino) 4 aminobenzene-3- sulphonic acid, 42.6 parts of 1-(3-acetoacetylamino-4- chlorobenzoylamino)-4-aminobenzene-3-sulphonic acid, 40.5 parts of 1-(3-acetoacetylamino-4-methylbenzoylamino)-4-aminobenzene-3-sulphonic acid, 42.1 parts of 1 3 acetoacetylamino-4'-methoxybenzoylamino -4-aminobenzene-3-sulphonic acid, 40.5 parts of, 1-(4-acetoacetylamino- 3-methylbenzoylamino)-4-aminobenzene-3- sulphonic acid, 40.5 parts of 1-(3- or -4-acetoacetylaminobenzoylamino)- 4 -arnino-5-rnethy1benzene-3-sulph,onic acid, 42.1 parts of 1-(3'- or #4-acetoacetylaminobenzoylan1ino)-4-amino-5- or -6-methoxybenzene 3 sulphonic acid, 42 parts of 3 or -4'-acetoacetylamino-4-amino-3- methyl-1.l'-diphenyl urea-S-sulphonic acid, 43.6 parts of 3'-acetoacetylamino 4 amino-Z- or -3-methoxy-1.1'-diphenyl urea-S-sulphonic acid, dyestufis are obtained which have a similar shade and similar good properties.

Example 5 21.6 parts of 2-amino-1-hydroxybenzene-4-sulphonic acid-dimethylamide are diazotised in the usual way and the diazo compound is poured into a solution of 40.6 parts of 4'-acetoacetylamino-4-amino-l.1-diphenyl urea- 3-sulphonic acid, 24 parts of sodium bicarbonate in 400 parts of water. The yellow monoazo dyestuff is isolated and further diazotised as described in Example 1. The neutralised diazonium compound is coupled with 29.7 parts of 1-amino-2-naphthylglycolic aCid-6-sulphonic acid in the presence of 20 parts of sodium acetate, the disazo dyestufi which is formed is dissolved with 5 parts of caustic soda, 400 parts of sodium chloride are added and the whole is diazotised at 20 with 8.2 parts of sodium nitrite and 60 parts of concentrated hydrochloric acid. On completion of the diazotisation, the diazo compound is filtered off and coupled with a solution of 41.2 parts of 2-(2.4-dichlorobenzoylamino) 6 hydroxynaphthalene-8-sulphonic acid, 20 parts of sodium carbonate and parts of pyridine. The green trisazo dyestutt of the formula:

HOOCCHQO is isolated with a little sodium chloride. When dry, it is a dark powder which dissolves in water with a green and in concentrated sulphuric acid with a greenish-brown colour. The after-coppered dyeings on natural or regenerated cellulose fibres have excellent light and acid fast ness properties.

It in this example, instead of 29.7 partsof 1-amino-2- naphthylglycolic acid-6-sulphonic acid the same number of parts of 1-amino-2-naphthylglycolic acid-7-sulphonic acid or 21.7 parts of l-amino-2-naphthylglycolic acid or OCHzCOOH OH 25.3 parts of l-amino2-n1ethoxynaphthalene-fior -7- sulphonic acid or 26.7 parts of l-amino-2-ethoxynaphthalene-6- or -7-sulphonic acid or 17.3 parts of l-amino- Z-methoxynaphthalene or 18.7 parts of 1-'1mino-2-ethoXynaphthalene, are used, dyestuffs of the same shade and similar properties are obtained. 7

9 10 Example 6 further diazotised as described in Example 1 and after 15.3 parts of 2-amino-1-hydroxybenzene-4-carboxylic filterlng Coupled With Parts of acid 111 the form of the chlorohydrate are dissolved in 200 benzovlammo)-6-hydr0Xynaphthalene-8-su1phonic acid parts of water, 10 parts of concentrated hydrochloric acid With the addjticm 20 Parts Of Sodium carbonate and are added and the Whole is diazotised with 6.9 parts of Parts py to form the green tTiSaZO y sodium nitrlte. This diazonium compound is coupled Stllfi 0f the 1011111113;

HO O 0 CH2? (13H H Q43 ONH--N=N -N=N -s 03H @rwrwon-o OlltH s 03H 1 OCH; 1.

NHCOCH: NH-CO with a solution of 34.8 parts of 4'-acetoacetylamino-4- After filtering and washing away the adhering impurities, ammod1phenyl-3-sulphonic acid in the presence of 30 a dark powder is obtained which dissolves in water with parts of sod ium carbonate and the yellow monoazo dyea green and in concentrated sulphuric acid with a brown stuff WhlCh 1s preclpitated with sodium chloride is filtered colour.

off. The dyestufi? is dissolved in 1000 parts of water and The dyestuff dyes natural or synthetic cellulose fibres diazotised as described in Example 1. The diazo suspena vivid green. The dyeings are made fast to washing, sion which is acid to Congo red is neutralised with 4 light and acid by after-treatment with copper salts on parts of sodium carbonate, and poured into a solution of the fibre. 21.7 parts of 1-amino-2-naphthylglycolic acid in 600 If in this example the 35.8 parts of 2(3-aminoparts of water to which has been added 20 parts of benzoylamino)-6-hydroxynaphthalene-8-sulphonic acid sodium acetate. On completion of the coupling, 400 are replaced by the corresponding number of parts of parts of sodium chloride are added and the disazo dye another of the acylated 2-amino-6-hydroxynaphthalenestuff is diazotised at 20-25 with 60 parts of concentrated S-sulphonic acids named in. Example 3, and otherwise hydrochloric acid and 8.2 parts of sodium nitrite. The the same procedure is followed, dyestuffs are obtained filtered diazonium compound is mixed into a solution of which have a similar shade and similar properties.

28.1 parts of 2-acetylamino-6-hydroxynaphthalene-8-sulphonic acid in 200 parts of water, 150 parts of pyridine and 20 parts of sodium carbonate. The trisazo dyestuft 46.7 parts of 4-(3"-acetoacctylaminobenzoylamino)- Example 8 of the formula: 4-aminodiphenyl-3-sulphonic acid are dissolved in 400 (|)H (])CH:COOH on N=NOHC ONH N=N N=N- s 0 311 to OOH (ll 03H Ha I NH-COOH:

is isolated as described in Example 1. When dry it is parts of water and 24 parts of sodium bicarbonate are a dark powder which dissolves in water with a yellowishadded. The diazonium compound made up from 22.4 green and in concentrated sulphuric acid with a brown parts of 6-chloro-2-amino-l-hydroxybenzenc-4-sulphonic colour. It dyes cotton and staple rayon in olive green acid which has been prepared in the usual way is added shades. The wet fastness of the after-coppered dyeings to this solution. The yellow monoazo dyestutf obtained is very good. is precipitated with sodium chloride and filtered off.

If in this example the 15.3 parts of 2-amino-l-hy- The filter cakes are dissolved in 1000 parts of water droxybenzene-4carboxylic acid are replaced by the and diazotised according to the method described in corresponding number of parts of another diazotised Example 1. After stirring for 4 hours, the neutralised Z-amino-l-hydroxybenzene derivative such as is listed suspension is poured into a solution of 2 9.7 parts of in Example 1, olive green dyestulfs are obtained which 1-am1no-2-naphthylglycol1c ac1d-7-sulpl1on1c acid to have similar properties. which has been added 20 parts of sodium acetate. The

Example 7 disazo dyestufi' obtained is violet and, with the addi ion of 400 parts of sodium chloride, is further drazotised 16.6 parts of 4acetylamino-2-amino-1-hydroxybenzene {50 with 8.2 parts of sodium nitrite and parts of hydroare dissolved in 200 parts of Water and 25 parts of chloric acid. It is filtered oit and finally coupled with concentrated hydrochloric acid and diazotised at 0 with an aqueous solution of 34.3 parts of Z-benzoylamino-d 6.9 parts of sodium nitrite. The diazonium body is hydroxynaphthalene-8-sulphonic acid, 20 parts of sodium coupled with an alkaline solution of 39.1 parts of 5-(3- carbonate and 150 parts of pyridine. The green trisazo acetoacetylaminobenzoylamino) 2 aminobenzenedyestuif of the formula:

01 OH N=N-ZHOOI] IH Hooooroo on O SOsH Q-o O-NH- -N=N -N=N -son1 I dour isn-oo l-sulphonic acid as described in example 1. The yelis precipitated with sodium chloride, filtered oil? and low monoazo dyestuff is isolated with sodium chloride, freed from impurities by washing. it is a dark powder dissolved in 1000 parts of water, 6.9 parts of sodium which dissolves in water with a green colour and in nitrite are added and the whole is added dropwise to concentrated sulphuric acid with a brown colour. 40 parts of hydrochloric acid. On completion of the After treatmentwith copper sulphate, the green dyediazotisation, the diazonium compound is filtered 01f ings obtained therewith on cellulose fibres have very and poured into a solution of 21.7 parts of l-aminogood fastness properties.

Z-naphthylglycolic acid to which 20 parts of sodium If instead of 46.7 parts of 4'-(3-acetoacctylaminoacetate have been added. The violet disazo dyestuff is benzoylamino)-4-aminodiphenyl-3-sulphonic acid, 48.3

parts of 4-( 1"-acetoacetylamino-3-mcthylbenzoyl- 20 parts of sodium acetate to form the violet disazo dyeamino)4-aminodiphenyl-3-sulphonic acid or 48.2 parts stuff. The reaction is made Weakly acid with parts of of 4'- 3"- or 4"-acetoacetylaminophenylureido)-4- sodium carbonate to accelerate the reaction. The disazo aminodiphenyl-3-sulphonic acid are used, or it instead dyestuff is diazotised according to the method given in of the 22.4 parts of 6-chloro-2-amino-l-hydroxybenzene- 5 Example 1 Finally, the isolated diazonium compound 4-sulphonic acid equivalent parts of another of the 2- is coupled with a solution of 28.1 parts of 2-acetylaminoamino-l-hydroxybenzene compounds listed in Example 6-hydroxynaphthalene-8-sulphonic acid in 200 parts of 1 are used, analogous dyestutfs with similar properties Water, parts of sodium carbonate and 150 parts of are obtained. pyridine to form the trisazo dyestufi of the formula:

Example 9 It is isolated with a little sodium chloride and when dry, it IS a dark powder which dissolves in water with a green an? in co i fienrated sulphuric acid with a yellowish-green co our. e yeings on cellulose fibres are green and on coupled with a soda alkaline solution of 40.6 parts of A 3 amino 4 acetoacetylamino 1.1-diphenyl ureaff- 3- 322;322 35 wlth Coppel Salts fast to fight Wash sulphonic acid. The precipitated monoazodyestu. is

filtered off, dissolved in 1000 parts of water and digi i i gg g'i giggff 23 g gggg f f g i azotised at 10-15 with 6.9 parts of sodium n1tr1te and B y am 40 anzene 1 sulphomc acid the same number of parts of parts of concentrated hydrochloric acid. After 4 acetoacetylamino 3n methylbenzoylamino) hours the dlazomum Compound 15 .made :Veakly acld benzoylamino]-2-aminobenzene-l-sulphonic acid or 51 to Congo red with 5 parts ot sodnlim carbgnate and parts of or 4,, acetoacetylaminobenzoyl added to g SOIL-mop 5 3 pansy? f naphtha? amino)-benzoylamino]-2-aminobenzene-l-sulphonic acid leneglycolic ac1d 1n parts or water with the addror 524 parts of y tion of 20 parts of sodium acetate. The whole is stirred b 1 b overnight and then the violet disazo dyestutf which enzoy ammo) enzoylammo] 2 ammobenzene 1 18.7 parts of 2-amino-1-hydroxybenzene-4-methyl sulphone are diazotised as described in Example 1 and forms is further diazotised the next day as described sulPhonic acid 525 P f 4'- (3"- Or 4-acetoa ;ety1- in Example 1. The dyestutf is isolated and coupled 9 Y P P Y with 31.3 parts of 2-carbethoxyamino-6hydroxynaphtha- P Q 391d 3251mm of 0T y lene-S-sulphonic acid in 200 parts of water, 150 parts ammo p y e y a ol 2 aminoof pyridine and 20 parts of sodium carbonate. After benzene-l-sulphonic acid, 53.9 parts of 5-[4'-(3"- isolating and washing free from impurities, the trisazo acetoacetylamino 4" methylphenylureido) benzoyldyestufi of the formula: amino]-2-armnobenzene-l-sulphonic acid or the same OH O'N=NZHCONH NHCONHQ oornooou on o AOzCH: I 80311 N=N --NN SOaH when dry is a dark powder which dissolves in water number of parts of 5-[4-(4"-acetoacetylamino-3"- with a green and in concentrated sulphuric acid with methylphenylureido) benzoylamino] 2 aminoa brown colour. Natural or regenerated cellulose fibres benzene-l-sulphonic acid are used, similar green trisazo are dyed green. On after-treating with copper salts, the dyestuffs With similar properties are obtained. dyeings are made fast to light, washing and acid.

If in this example, the 18.7 parts of Z-amino-l-hy- Example 11 droxy-benzenel-methyl sulphone are replaced by the corresponding number of parts of another 2-amino-1- 18.8 parts of 2-amino-l-hydroxybenzene-4-sulphonic hydroxybenzene derivative listed in Example 2, similar acid amide are diazotised and coupled with 39.1 parts green dyestuffs with similar properties are obtained. of 5 (3' aminobenzoylamino) 2 acetoacetylamino- Emmple 10 ben zene-1-sulphonic acid in 400 parts of water with the addition of 24 parts of sodium bicarbonate to form the 18.9 parts of 3-amino-4-hydroxybenzene-l-sulphonic yellow monoazo dyestufi. This is precipitated with 200 acid are dissolved at 20 in 180 parts of water with 4.1 parts of sodium chloride, dissolved at 60 in 1000 parts parts of caustic soda, mixed with 30 parts of concentrated of Water and mixed with 6.9 parts of sodium nitrite, after hydrochloric acid and diazotised by the addition of 6.9 which the whole is poured into 40 parts of concentrated parts of sodium nitrite. The diazonium compound is hydrochloric acid. On completion of the diazotisation,

coupled with 52.4 parts of 5-[4-(3-acetoacetylarnino- 4 parts of sodium carbonate are added until the reaction 4 methylbenzoylamino) benzoylamino] 2 aminois weakly acid to Congo red and the suspension is poured benzene-l-sulphonic acid in 600 parts of water and 30 into a solution of 29.7 parts of l-amino-Z-naphthylparts of sodium carbonate to form a yellow monoazo glycolic acid-6-sulphonic acid in 600 parts of water and dyestutt'. After isolating this dyestutt, it is dissolved in 20 parts of sodium acetate. The violet disazo dyestutr- 1000 parts of water and further diazotised with 6.9 parts is further diazotised as described in Example 1, filtered of sodium nitrite and 40 parts of concentrated hydroand poured into a solution of 39.3 parts of 2-(4-chlorochloric acid. The isolated diazonium compound is cou- 3' amlnobenzoylamino) 6 hydroxynaphthalene 8 pled with 25.3 parts of 1-amino-2methoxynaphthalenesulphonic acid, 20 parts of sodium carbonate in 200 6-sulphonic acid in 200 parts of water in the presence of parts of water and parts of pyridine.

13 The green trisazo dyestuif of the formula:

| SOZNHQ l SOsH CHa It in this example the 39.1 parts of 5-(3-a1ninobenzoylr amino)-2-acetoacetylaminobenzene-l-sulphonic acid are replaced by 40.5 parts of 5(4'-amino-3-methylbenzoylamino)-2-acetoacetylarninobenzene-l-sulphonic acid, 40.6 parts of 3'- or 4'-amino-4-acetoacetylamino-1.1'-diphenyl urea-3-sulphonic acid, 42.6 parts of 5-(3-ami11o-4'- chlorobenzoylamino) 2 acetoacetylarninobenzene l-sulphonic acid, 40.5 parts of 5(3-amino-4'-methylbenzoylamino) 2 acetoacetylaminobenzene 1 sulphonic acid, 42.1 parts of 5-(3'-amino-4-methoxyn benzoylamino) 2 acetoacetylaminobenzene 1 sulphonic acid, 45.3 parts of 5-(3-aminobenzoylamino)- 2-benzoylacetylarninobenzene-l-sulphonic acid, 46.7 parts of 5- (4arnino-3 -methylbenzoylamino -2-benzoylacetylaminobenzene-l sulphonic acid, or 42 parts of 3-amino- 4 acetoacetylamino 3 methyl 1.1 diphenylurea 5 sulphonic acid, similarly good dyestuffs of a similar shade are obtained.

H acyl Example 12 1.5 parts of the dyestulf obtained according to Example 1 are dissolved in a dyebath containing 3000 parts of water and 2 parts of soda. 100 parts of cotton are entered'at 40-50", the bath is heated to 9095 within wherein A represents an aromatic radical of the benzene oorno 0 OH OH N=N 803E.

ITIH: lltH-O 06-01 series containing the hydroxyl group in the o-position to the azo linkage, B stands for the group SOaH each of n and m is one of the numbers 0 and 1, each of U and V represents an aromatic radical of the benzene series in which the bonds shown stand. in other than the o-position of said aromatic radicals and which are free from carboxylic acid and sulphonic acid groups, X represents a bridging member selected from the group consisting of the direct carbon-carbon linkage and the groups C0-NH and -NH-CO--NH-, acyl represents a member selected from the group consisting of alkoyl and benzoyl radicals, Y represents a member selected from the group consisting of alkoxy and -OCH2COOH groups, one Z represents hydrogen and the other Z represents a member selected from the group consisting of hydrogen and the sulphonic acid group, and R represents a carboxylic acid acyl radical bound directly to the adjacent --NH- group by the -CO group.

2. A trisazo dyestuif which corresponds to the formula SOaH Y wherein A represents an aromatic radical of the benzene to the azo linkage, V represents an aromatic radical of the benzene series in which the bonds shown stand in other than the o-position of said aromatic radical and which is free from carboxylic acid and sulphonic acid minutes, 30 parts of sodium sulphate are added and groups X represents a bridging member Selected from dyeing is performed for 45 minutes at this temperature. After this time, the dyed goods are rinsed cold and aftertreated at 70 in a fresh bath with Zparts of crystallised copper sulphate in 2000 parts of water and 2 parts of 30% acetic acid for half an hour. are rinsed and dried in the usual Way. The cottom is dyed in green shades which have excellent fastness properties.

What We claim is:

1. A trisazo dyestuif which corresponds to the formula 65 S 0311 acyl 0 H aeyl the group consisting of the direct carbon-carbon linkage and the groups -CONH and -NH-CO NH--, acyl represents a member selected from the group consisting of alkoyl and benzoyl radicals, Y represents a The goods member selected from the group consisting of alkoxy and OCH2COOH groups, one Z represents hydrogen and the other Z represents a member selected from the group consisting of hydrogen and the sulphonic acid group, and R represents a carboxylic acid acyl radical bound directly to the adjacent -NH group by the -CO- grou 3. A trisazo dyestufi? which corresponds to the formula SOaH Y 15 wherein A represents an aromatic radical of the benzene series containing the hydroxyl group in the o-position to the azo linkage, V represents an aromatic radical of the benzene series in which the bonds shown stand in m-position of said aromatic radical and which is free from carboxylic acid and sulphonic acid groups, X represents a bridging member selected from the group consisting of the direct carbon-carbon linkage and the groups --CONH and -NHCO--NH-, acyl represents 16 g a member selected from the group consisting of alkoyl and benzoyl radicals, Y represents a member selected from the group consisting of alkoxy and OCH2COOH groups, one Z represents hydrogen and the other Z represents a member selected from the group consisting of hydrogen and the sulphonic acid group, and R represents a carboxylic acid acyl radical bound directly to the adjacent NH group by the CO- group.

4. The trisazo dyestuif of the formula:

N=N(i'1H-COIIIH HOOCCHKI) OH OsH 403E NHco- 5. The trisazo dyestufi of the formula:

SOzCHa SOzOHt l OOHa NBC 0 CH:

0 (11320 O OH OH NH-OO-O-CHzGHs 6. The trisazo dyestufi of the formula:

S OaH 8. The trisazo dyestuff of the formula:

,HOOCCHzO NHn References Cited in the file of this patent UNITED STATES PATENTS 1,594,865 Zitscher Aug. 3, 1926 2,115,412 Dahlen et al Apr. 26, 1938 2,515,546 Bossard et a1. July 18, 1950 FOREIGN PATENTS 367,675 Great Britain Feb. 25, 1932 

1. A TRISAZO DYESTUFF WHICH CORRESPONDS TO THE FORMULA 